Plasticizers



Patented May 25, 1948 PLASTICIZERS Eugene Lieber, New York, N. Y., assignor to Standard Oil Development Company, a corporation of Delaware No Drawing. Application August 28, 1943, Serial No. 500,431

2 Claims. (Cl. 250-479) This invention relates to the manufacture of a new composition of matter and, more particularly, the manufacture of new compositions that are especially adapted for use as plasticizers.

A plasticizer may be defined as a non-volatile,

non-separating neutral substance which when added to another material imparts plasticity to the mixture; Plasticizers of the solvent type having a very low volatility cause the plasticized film to flow and give without rupture under stress. It allows for film elongation and contraction with changes in temperature and permits bending and yielding without fracture under impact. 1. Mellan, in his book entitled Industrial Solvents published by Reinhold Publishing Company, in chapter 16, summarized the requirements of a good plasticizer as follows:

1. Good solubility for the material it is used to plasticize, as cellulose derivatives, gums, resins and so forth.

2. Little or no inflammability.

3. Clear, colorless or nearly so. If it'contains color, it should not interfere with the finished product. v i 4. Odorless and tasteless or nearly so, especially when it is used for wrapping food products.

5. Should be unafiected by light, water, chemicals, oils and fats.

6. Stable to atmospheric conditions.

7. Must not crystallize or separate. stay in solution permanently.

8. Should possess a high melting be non-volatile.

9. Neutral or nearly so.

10. Relatively inexpensive.

11. Must not impair hardness of film, nor'plastic mass, nor have bubbling qualities.

12. Should not increase viscosity; if anything, it should decrease it.

13. Should impart ductility, tenacity and adherence.

14. Non-conductor.

1 5. Compatible with filler, dye, pigments and resins.

16. Must produce highly elastic, non-shrinking and non-scratchable surface.

17. Must produce a homogeneous, tough, flex- It must ible and permanent film and should not appreciably reduce film strength.

point and 2. 18. Should be non-injurious to film or plastic mass.

19. Non-hydrolyzing.

20. Resistant to heat, or be heat-proof.

21. Flexibility -at all temperatures.

22. High retentivity.

23. Stability on aging.

It has been found impossible and unnecessary for any substance to meet all the above requirements, but as the purpose and use to which the plasticized material will be subjected determines the properties thatare necessary in the finished material, different plasticizers or mixtures of different plasticizers are used.

This invention has for its object the preparation of new plasticizers from petroleum hydrocarbons.

According to the present invention substances of the general formula (R n-RR-(ORP) m are eflective plasticizers R =an alkyl radical derived from petroleum hydrocarbons R==an aryl nucleus O=oxygen R =an acyl radical m, n=integers whose value may be one or more.

Typical examples of this class of substances are the following:

o .o 0 .CH;

White oil "White oil-phenol-acetate" War --0 0 C .CIHI 40 Wex-naphthol-propionate" Kerosen -O 0 C C "H" 5 "Keryl-resorclnol-mono-stemte" 0.0C.CH:

Keryl-resol'cinoldiacetate' Products of the type of where R is an alkyl radical derived from petro- Exam A kerosene was chlorinated to 16% chlorine content by passing chlorine gas through kerosene at a temperature of 200 F. One hundred sixtynine grams of ZnClz was finely powdered and contained in a 2-liter-3-necked Pyrex round bottom flask fitted with a mechanical stirrer, thermometer, and reflux condenser. The stirrer was started and 600 grams of molten phenol added. The reaction on on Kerosen Kerosene-Cl ZnCl: H01

takes place readily, a vigorous evolution of HCl taking place at 120 F. The reaction mixture was heated following the schedule set forth below:

- '4 The reaction mixture was allowed to cool and 500 cc. of aqueous HCl was added. The mixture was poured into a separatory funnel and washed twice with hot 20% aqueous 1101 followed by four washes with hot water, It was then distflledwith fire and steam as follows:

Fraction I=steam in at 220 F. to 360 F. Fraction n=seo- F. to 450' F.

Fraction m=o F. to 650 F.

Residue=black resinous material=26. grams.

Fractions I and II were combined and consisted of unreacted kerosene and phenol, After separating from the steam condensate this weighed 181-grams.

Fraction III comprised the keryl-phenol cut mixed with 600 grams of the chloro-kerosene weighed 423 grams. This was found to have an Kerosene The entire fraction was dissolved in benzol, separated from the steam condensate, and the benzol extract distilled to remove the benzol, the objective being to dry the keryl-phenol." The last traces of benzol were taken off under high vacuum. The dried keryl-phenol fraction acetyl value" of 160 which means that the product has the composition Proceeding in the same fashion described in Example 1, other alkylated phenols were made by using such petroleum fractions as gas oil, various white oils of low and high viscosity, paraflln wax, T Elapsed Time Temps sweater oil, refrigerator oil and a lubricating oil, 59 The experimental data for the preparation of 5" 35m $52 these alkylated phenols are summarized in the 5 280 attachedTable I, while Table II summarizes the g g 5 35 min 340 acetyl values found for these materials. The 1 acetyl values are expressed as milligrams of po- 55 tassium hydroxide required to saponify one gram 1 Cut heat of acetylated material.

TABLE I Alkylated phenols-summary of preparations Alkylating Agent Reaction 13 I r c t 131 l z $1 1? er en Grams n Tom Time Petroleum Hydrocarbon s l Used s 8 Kerosene 16 e00 600 169 340 s I 423 Gas Oil 16 800 900 200 350 3 53s Bayol-D 17 800 900 200 350 1% 609 w 16 800 900 200 350 1% e14 40Vis. White 0 16 800 900 200 350 2 54s Refrigerator Oil 16 800 900 200 350 1% 505 Sweater Oil is 800 000 200 350 1% s05 Lubricating on I is e00 925 200 245 1% 813 l Bayol-D is a ht white oil, 13. P. 400-500 F. and 31,8 Saybolt viscosity at F.

ints

1 Melting v I Aneutraf having a viscosity-oi 44 seconds Saybolt at 210 F.

TABLE II Alloylated phenols-summary of acetyl values A similar experiment was with the same chloro-kerosene and resorcinol and a high yield of "keryl-resorcinol Kerosene v was obtained.

The keryl-phenols" so obtained are readily esterified. Thus, by treating keryl-resorcinol with acetyl chloride a quantitative yield of kerylresorcinol-diacetate 0.0C.CH:

--0.0C.CHs

Kerosene was obtained. Since the kerosene radical in the above compound averages carbon atoms, the following comparison between butyl acetyl ricinoleate and keryl-resorcinol-diacetate can be made:

The keryl-resorcinol-diacetate" so produced is an excellent plasticizer for cellulose products and other materials.

Alternatively,

Diamyl phenol ..lbs.. 234 Glacial acetic acid (5% excess) lbs 63 sulfuric acid lbs..- 2 m Benzol -ga1s.. 70 Soda ash lbs 5 are used. 1

The diamyl phenol, acetic acid and benzol are 15 placed in the esterification reactor, followed by the sulfuric acid. Reaction is eflected by heating to reflux. The water of esterlflcation is removed as an. azeotrope and is drawn oil inthe separator, while the benzol is returned to the reactor.

of diamyl phenol used is recovered when esteriiying. There will be a slight excess of water over the theoretical, due to water being contained in the reagents. The reaction is complete when water'no longer separates from the benzol on con densation. The reaction mixture is then neutralized with the soda-ash (aqueous solution) and, after washing, the benzol is removed by distillation. This operation also dries the crude product. The benzol recovered is recycled.

The crude product is purified by subjecting to a-vacuum distillation at 540mm. absolute H pressure, which yields the following:

Fraction I (forerun) =up to 140 C.==10 lbs. Fraction II (product) =140 to 160 C.=250 lbs. Residue=16 lbs.

The yield is of theory based on the'diamyl phenol used.

The properties of synthetic plasticizers as obtained are as follows:

45 Saponification number 179.6 Free organic acidity 0.06 Refractive index at 25 C 1.5001 Color INPA or better Specific gravity at 25/15" C 0.951

, 50 Ash None Saybolt vls. at F 1'74 Solubility in ethyl alcohol Soluble at 25 C.

Solubility in Glac. acetic acid--- Soluble at 25 C. Solubility in ASTM naphtha--- Soluble at 25 C.

The attached Table III illustrates the properties of various plasticizers prepared according to this method: a

.Butyl-Acetyl-Ricinoleate Keryl-Resorclnol-Diaeetate,

Structural Formulae Co u.CHLCH:.CH:CH.0111 413000 11.

Em irical Formula.... 0141314 04 Mo ecular Weight.-..- 397 Acyl Groups- 2 Saponification Value... 282

OAc

OAc

Onepound mole oi! water (2.16 gals.) per pound-mole Plseticizer A B O Seponiflcation Value 161.2. 06.3- 128. Free Acidity as Oleic Acid 0.07%. 0.96% N n A. s. '1, M. Solid Point 60 F 50 F -46 F specific Gravity at 25/15" 0.984. o 1172 03m iscosity at 100 F. (Saybolt) 104.2- 59 166.4, N. P. A. Color 5 1% 2}. Boiling Range (-15 mm.) C... 100400 100-250 150-275 MIL NW6 None None, Rehactlve Index at C 1.5123 1.4830 1.6013 Solubilities at 25 0.:

95 Ethyl Almhnl soluble Solubl Soluble.

G Acetic Acid. do Do.

A. 8. T. M. N aphth do do Do.

Chemical Designation Kero-Phenyl-Acetate Beyol-D-Phenyl-Acetate Bagil -D Phcnyl- Acetate 1 (Low Vls.). igh Via.)-

Structure I OAc 0 Ac OAc Kerosene Bayol-D Bayol-D Plasticizer D E F Sponifl Value. 40.5 177. Free Acidity as Oleic Acid 0.01% 0.03%. A. S. T. M. Solid P in 0 F 5 F. Specific Gravity at 25/l5 O. 0.881 1.022. Viscosity at 100 F. (Saybolt)-. 86.9--- 453.7. N. P. A. Color 3 1%. Boiling Range (10-15 mm.) C 175-290 175-195 Ash Non None. Rol -active Index at 25 C 1.4850 1.5454. Solubillties at 25 0.:

95% Ethyl Alcohol Insoluble Soluble.

Glacial Acetic Acid--. d Do.

A. B. T. M. Naphtha. Soluble ..do Do. Chemical Designaticn Bayol-FePhenyl-Acetater Diamyl-Phenyl-Acetate- Diamyl-Phenyl Benzoate.

Structure 1 Ac-ace lradlcle-CHaCO- Bsyol-F a light white oil, B. P.-570 to 690 F. having a Saybolt viscosity of 52 at 100 F.

The plasticizing properties of O:C.CH: Bayol-D "Bayol-D-phenyl-acetate" and Diamyl-phenyl-acetate" at and above 5% concentration, while diamylphenyl-acetate" produced no haze up to 20%.

The percent compatibility with cellulose acetate was determined by a modified dilution ratio test" which is carried out as follows:

To 2 grams of cellulose acetate is added 20 cc. of acetone and 2 cc. of the plasticizer in question. A blank is also made using 2 cc. of acetone in place of the plasticizer. The solutions are then titrated with toluene to the point at which pre- 'cipitation occurs. The number oicc. of toluene added is an indication of the compatibility of the plasticizer with cellulose acetate. ratio is expressed as: cc. toluene used/cc. solvent has the smallest compatibility.

The cellulose acetate used in the above tests is Hercules grade #LL-l. Solutions for the film tests" described above were made in the following: I

Per cent by volume Acetone 24 .Methyl ethyl ke' 55 Methyl cellosolve acetate 10 Ethyl lactate 11 so as to contain 10% solids. To this were added various concentrations of plasticizer.

I claim:

1. Process of preparing a composition which comprises chlorinatlng a kerosene until it has a 16% chlorine content in forming chloro-kerosene, refluxing the chloro-kerosene with phenol in the presence of a condensation catalyst, cooling the resulting condensation product mixture The dilution.

. I 9 I V and washing with aqueous hydrochloric acid, and distilling the mixture to obtain a. fraction boiling between 450 and 650 F.,and subsequently esteri tying said distillation fraction of the mixture with an organic carboxyiic acid.

2. Process according to claim 1 in which zinc chloride is used as condensation catalyst.

EUGENE LI'EBER.

REFERENCES CITED The following references are of record in the file of this patent:

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